CHEMISTRY OF THE

MAIN GROUP
ELEMENTS
GROUP 1,2 AND 13 - 18
PROF F. NAREETSILE
INORGANIC CHEMISTRY LECTURER/RESEACHER

OFFICE NO: 237-249

TEL: 355-2488 (W)

EMAIL: [email protected]
MAIN GROUP ELEMENTS

Consist of the s- and p-block elements

s- block: Groups 1 and 2
•The s-block elements are the alkali metals and
alkaline earth metals.
p-block: groups 13 to 18 (III to VIII)
•are the basic metals, metalloids, nonmetals, halogens,
and noble gases
 GENERAL PROPERTIES OF THE S-BLOCK
ELEMENTS
Possess one oxidation state
•general valence configuration is ns1–2.
•Oxidation state of +1 for Group 1
•Oxidation state of +2 for group 2
Most of them are highly reactive
•Reductants
They are soft
•Low melting and boiling points
They are highly electropositive
•Form ionic compounds
Have characteristic colour to a flame
•Important in qualitative analysis
GENERAL PROPERTIES OF THE P-
BLOCK ELEMENTS
Have variable oxidation states
•Sulfur has -2, 0, +2, +4 and +6 oxidation states
Valence electrons ns2np1-6
Group 17 has -1 oxidation state
Group 18 has 0 oxidation state
Their properties range from non-metals, metallic
and metalloids depending on the group
QUESTIONS

• Write the valence shell electronic configuration for groups

1, 2, 13 to 18.
GROUP I ELEMENTS
OCCURENCE
• Na as rock salt (NaCl)
• Na, K in natural brines and sea water
• Rb, Li and Cs found in various silicate minerals
DOWNS CELL FOR THE ELECTROLYSIS OF MOLTEN SODIUM. THE IMAGE IS TAKEN
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%3A_CHEMISTRY_-_THE_CENTRAL_SCIENCE_(BROWN_ET_AL.)/
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EXAMPLES OF GROUP I
COMPOUNDS
• Halides
• Hydroxides
• Hydrides
• Oxides-they are basic when dissolved in water
• Most of the salts conduct electricity
GROUP TRENDS

• Electronic Configurations
• Atomic and ionic sizes
• Ionization Energies
• Chemistry
• Anamolous behaviour of the 1st element I the group
 Group I – Alkali metals

Li 1s22s1 or[He] 2s1

Na 1s22s22p63s1 or[Ne] 3s1
K 1s22s22p63s23p63d104s1 or[Ar] 4s1
Rb 1s22s22p63s23p63d104s24p64d105s1 or[Kr] 5s1
Cs 1s22s22p63s23p63d104s24p64d105s25p66s1 or[Xe] 6s1
Fr or[Rn] 7s1
GROUP I ELEMENTS

• They are all metals

• Have ground state valence electron configuration ns1
• Form simple compounds and mostly ionic
• Hydroxides and oxides form very strong bases

• Fr is heaviest member and is radioactive (t1/2 = 21.8 min)

GENERAL TRENDS

• (i) Atomic and Ionic Radii

• (ii) Ionization Energies
• (iii) Oxidation States
• (iv) Anomalous behaviour of Li
• (v) Diagonal Relationship between Li and Mg
 ATOMIC AND IONIC RADII
For atoms

r atom= ½ x 2r
↔
2r

For ions r = share of a distance of an ion between

neigbouring anions
ATOMIC AND IONIC RADII

Atom Atomic radius Ionic radius

(Ao) (Ao)
Li 1.52 0.76
Na 1.86 1.02
K 2.27 1.38
Rb 2.48 1.52
Cs 2.65 1.67
ATOMIC AND IONIC RADII

• Group 1 are the largest in their periods in the periodic table

• Increases down the group due to occupation of higher shells
on going down the group.
• Ionic radii also increases down the group but smaller than
that of the counter atomic size, WHY?
IONIZATION ENERGIES (I.E.)

Element 1st I.E. (kJ/mol) 2nd I.E.(kJ/mol)

Li 520.1 7296

Na 495.7 4563

K 418.6 3069

Rb 402.9 2650

Cs 375.6 2420
1ST IONIZATION ENERGIES (I.E.)

• I.Es of the group 1 are the lowest in their periods .

• Atoms very large and thus outer electron is
loosely held by the nucleus and hence less energy
is needed to remove the elcron
• On going down the group, atomic sizes increase
and the outermost electron become less strongly
held and thus I.E decreases
2ND I. ES

• Also decrease on going down the group

• In comparison to 1st I.E. it is very high why?
• 2nd electron is being removed from a closed shell.
ANOMALOUS BEHAVIOUR OF
LITHIUM
• Have same valence electrons as group 1 elements but
different chemical properties from rest of the group-
anomalous behaviour.
• Small compared to the rest of the members
• Resembles Mg in many aspects- diagonal relationship
 FLAME TESTS
Element Colour of Flame

Li Crimson

Na Yellow

K Lilalic

Rb Red violet

Cs Blue

Used in qualitative analysis of Group I M+ ions

APPEARANCE OF GROUP I
METALS
GROUP II METALS- ALKALINE EARTH
METALS
Element Symbol Electronic
Configuration
Beryllium Be [He] 2s2

Magnesium Mg [Ne] 3s2

Calcium Ca [Ar] 4s2

Strontium Sr [Kr] 5s2

Barium Ba [Xe] 6s2

Radium Ra [Rn] 7s2

TRENDS IN ATOMIC AND IONIC SIZES

Element Atomic radius Ionic radius M2+

(Ao) (Ao)
Be 1.12 0.45
Mg 1.60 0.72
Ca 1.97 1.00
Sr 2.15 1.18
Ba 2.22 1.35
Ra - 1.48
TRENDS IN I.E.S

Element 1st I.E. 2nd I.E. 3rd I.E.

Be 899 1757 14 847
Mg 737 1450 7 731
Ca 590 1145 4910
Sr 549 1064
Ba 503 965
Ra 509 979 (3 281) est.
Sight increase in Ra 2nd i. e due to lanthanide contraction.
TRENDS IN I.E.S

• Same trends as observed for Group 1.

• Form divalent compounds because it is easier to remove the
two outer electrons
• Third electron is removed from a closed shell hence the big
jump in energy.
• Can not form MX compounds because lattic energy for
MX2 offsets the I.Es
 BERYLLIUM
Be shows differences to the rest of the group, in fact it shows remarkable
differences than Li show with group I metals.
Reasons: Be atom and Be2+ ion are both extremely small.

The relative increase in size from Be2+ to Mg2+ is four times greater
than the increase between Li+ and Na+.
Be shows some diagonal relationship with aluminum in Group III
Fajan’s rules state that small highly charged (high charge density)
ions tend to form covalent compounds

Be has a comparatively high electronegativity (EN).

When Be reacts with another atom the EN difference is not large which
favours the formation of covalent compounds.

Examples : BeF2, EN difference < 2.0

BeO, EN difference < 2.0
These show evidence of covalent character
 Beryllium – differences
Be – very small – high charge density – strong tendency to form covalent bonds

BeH2 – electron deficient, polymeric, multicenter bonding

(similar to aluminium hydride)

H H – hydrogen bridges –
H
Be Be Be Be
3c-2e bonds.
H
H H Be – 2 valence electrons
and H only one

BeCl2 – forms chains – exists also as dimer. AlCl3 is also dimeric

Cl
Cl Be Cl Cl Be Be Cl
Cl

Cl Cl
Cl
Be Be Be Be
Cl
Cl Cl
 IONIZATION ENERGY

Ionization Energy (kJmol-1)

1st 2nd 3rd

Be 899 1757 14847

Mg 737 1450 7731
Ca 590 1145 4910
Sr 549 1064
Ba 503 965
Ra 509 979
Why is the 1 IE for group II higher than 1st IE for group I? (3 marks)
st

M3+ ions are never formed

Be2+ compounds typically covalent

Mg also forms some covalent compounds

Mg, Ca, Sr and Ba predominantly divalent and ionic

Total energy required to produce a divalent gaseous ion is

large (compare with +1 ions of Gp1 – four times the energy
required for the formation of M+ in Gp1).
 ELECTRONEGATIVITY
Electronegativity values are low (but higher than Gp 1)

Compounds with halogens (Cl, F, Br) and oxygens are ionic

Electronegativity of Be higher (compared to other elements in the group)

and tend to form covalent compounds (BeF2 also regarded as covalent)